The present study evaluated the effect of using electrospun polycaprolactone (PCL) as a barrier coating and black pepper oleoresin (OR) as a natural extract on the morphology, thermal, mechanical, antimicrobial, oxygen, and water vapor barrier properties of solvent cast gelatin (GEL). The antimicrobial activity of the developed multilayer system obtained by the so-called electrospinning coating technique was also evaluated against Staphylococcus aureus strains for 10 days. The results showed that the multilayer system containing PCL and OR increased the thermal resistance, elongated the GEL film, and significantly diminished its permeance to water vapor. Active multilayer systems stored in hermetically closed bottles increased their antimicrobial activity after 10 days by inhibiting the growth of Staphylococcus aureus. This study demonstrates that addition of electrospun PCL ultrathin fibers and OR improved the properties of GEL films, which promoted its potential use in active food packaging applications.